JPH0375561B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-resistant composition, more specifically, (A) a copolymer of a vinyl ester and an olefinic unsaturated monomer having a silyl group in the molecule represented by the following general formula () or (). A modified polyvinyl alcohol which is a saponified product and contains 0.1 to 2.5 mol% of a monomer unit having a silyl group in the molecule, and (B) a water-insoluble inorganic substance containing aluminum, silicon, magnesium or calcium element. Therefore, the weight ratio of (A) and (B) is (A)/(B)=1/
The present invention relates to a water resistant composition characterized in that the water resistance is 99 to 90/10. [Here, n is an integer of 0 to 4, m is an integer of 0 to 2, R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is an alkoxyl group or acyloxyl group having 1 to 40 carbon atoms (here, an alkoxyl group) , the acyloxyl group may have an oxygen-containing substituent). ] [Here, m is an integer of 0 to 2, R ¹ is a carbon number of 1 to
5 alkyl group, R ² is an alkoxyl group or acyloxyl group having 1 to 40 carbon atoms (the alkoxyl group or acyloxyl group may have an oxygen-containing substituent), R ³ is a hydrogen atom or a methyl group , R ⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkylene group having 1 to 5 carbon atoms, or a divalent organic residue in which chain carbon atoms are interconnected by oxygen or nitrogen. show. ] Polyvinyl alcohol (hereinafter abbreviated as PVA) has been widely used as various binders, adhesives, and surface treatment glues, and it has excellent film-forming properties and strength that are unrivaled by other glues. It is known to have excellent performance. However, since PVA is water-soluble, it has the disadvantage of low water resistance, and although various methods have been studied to improve this problem, the current situation is that none of them are satisfactory. As a result of intensive studies aimed at overcoming the drawbacks of PVA described above, the present inventors found that (A) a vinyl ester and an olefinic unsaturated monomer having a silyl group in the molecule represented by the following general formula () or (). Modified PVA which is a saponified product of a copolymer with PVA containing 0.1 to 2.5 mol% of monomer units having a silyl group in the molecule, and (B) containing aluminum, silicon, magnesium or calcium elements. It consists of water-insoluble inorganic substances, and the weight ratio of (A) and (B) is (A)/(B)=1/
It has been discovered that a water-resistant composition characterized by a ratio of 99 to 90/10 has extremely excellent water resistance, and the present invention has been completed. [Here, n is an integer of 0 to 4, m is an integer of 0 to 2, R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is an alkoxyl group or acyloxyl group having 1 to 40 carbon atoms (here, an alkoxyl group) , the acyloxyl group may have an oxygen-containing substituent). ] [Here, m is an integer of 0 to 2, R ¹ is a carbon number of 1 to
5 alkyl group, R ² is an alkoxyl group or acyloxyl group having 1 to 40 carbon atoms (the alkoxyl group or acyloxyl group may have an oxygen-containing substituent), R ³ is a hydrogen atom or a methyl group , R ⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkylene group having 1 to 5 carbon atoms, or a divalent organic residue in which chain carbon atoms are interconnected by oxygen or nitrogen. show. ] The present invention will be explained in more detail below. First, it is a saponified product of a copolymer of vinyl ester (A) of the present invention and an olefinic unsaturated monomer having a silyl group in the molecule represented by the general formula () or (), which has a silyl group in the molecule. A method for producing modified PVA containing 0.1 to 2.5 mol% of monomer units having silyl groups will be explained. In the method of saponifying a copolymer of a vinyl ester and an olefinic unsaturated monomer having a silyl group in the molecule represented by the following general formula () or (), for example, the vinyl ester and the By copolymerizing a silyl group-containing olefinic unsaturated monomer using a radical initiator, and then adding an alkali or acid catalyst to an alcohol solution of the copolymer to saponify the copolymer. Silyl group-containing modification
You can get PVA. [Here, n is an integer of 0 to 4, m is an integer of 0 to 2, R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is an alkoxyl group or acyloxyl group having 1 to 40 carbon atoms (here, an alkoxyl group) , the acyloxyl group may have an oxygen-containing substituent). In addition, if two R ^1s exist in the same monomer,
R ¹ may be the same or different. Furthermore, when two or more R ² exist in the same monomer, R ² may be the same or different. ] [Here, m is an integer of 0 to 2, R ¹ is a carbon number of 1 to
5 alkyl group, R ² is an alkoxyl group or acyloxyl group having 1 to 40 carbon atoms (the alkoxyl group or acyloxyl group may have an oxygen-containing substituent), R ³ is a hydrogen atom or a methyl group , R ⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkylene group having 1 to 5 carbon atoms, or a divalent organic residue in which chain carbon atoms are interconnected by oxygen or nitrogen. show. In addition, if two R ^1s exist in the same monomer,
R ¹ may be the same or different. Furthermore, when two or more R ² exist in the same monomer, R ² may be the same or different. ] Vinyl esters used in the above method include vinyl acetate, vinyl propionate, vinyl formate, etc., but vinyl acetate is preferred from an economical standpoint. Specific examples of the vinylsilane represented by the above formula () include vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltris-(β
-methoxyethoxy)silane, vinyltriacetoxysilane, allyltrimethoxysilane, allyltriacetoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinyldimethyl Acetoxysilane, vinylisobutyldimethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltrihexyloxysilane, vinylmethoxydihexyloxysilane, vinyldimethoxyoctyloxysilane, vinylmethoxydioctyloxysilane, vinyltrioctyloxysilane , vinylmethoxydilauryloxysilane, vinyldimethoxylauryloxysilane, vinylmethoxydioleyloxysilane, vinyldimethoxyoleyloxysilane, and further general formula (Here, R ¹ and m are the same as above, and x is an integer of 1 to 20.) Polyethylene glycolized vinylsilane and the like can be mentioned. Further, specific examples of the (meth)acrylamide-alkylsilane represented by the formula () include:
3-(meth)acrylamide-propyltrimethoxysilane, 3-(meth)acrylamide-propyltriethoxysilane, 3-(meth)acrylamide-propyltri(β-methoxyethoxy)
Silane, 2-(meth)acrylamido-2-methylpropyltrimethoxysilane, 2-(meth)acrylamido-2-methylethyltrimethoxysilane, N-(2-(meth)acrylamido-ethyl)-aminopropyltrimethoxysilane , 3-
(meth)acrylamide-propyltriacetoxysilane, 2-(meth)acrylamide-ethyltrimethoxysilane, 1-(meth)acrylamide-methyltrimethoxysilane, 3-(meth)acrylamide-propylmethyldimethoxysilane, 3-(meth)acrylamide-propylmethyldimethoxysilane, ) acrylamide-propyldimethylmethoxysilane, 3-(N-methyl-(meth)
acrylamide)-propyltrimethoxysilane,
3-((meth)acrylamide-methoxy)-3-
Hydroxypropyltrimethoxysilane, 3-
((meth)acrylamide-methoxy)-propyltrimethoxysilane, dimethyl-3-(meth)acrylamide-propyl-3-(trimethoxysilyl)-propylammonium chloride, dimethyl-2-(meth)acrylamide-2-methylpropyl -3-(trimethoxysilyl)-propylammonium chloride and the like. In addition, when copolymerizing the vinyl ester and the olefinic unsaturated monomer containing a silyl group to produce the modified PVA used in the present invention, it is necessary to use monomers other than the above two components. Other unsaturated monomers copolymerizable with the polymer, such as styrene, alkyl vinyl ether, vinyl versatate, (meth)acrylamide, olefins such as ethylene, propylene, α-hexene, α-octene, (meth)acrylic acid , crotonic acid, (anhydrous)
Unsaturated acids such as maleic acid, fumaric acid, itaconic acid, and their alkyl esters and alkali salts, 2
-Sulfonic acid-containing monomers such as acrylamide-2-methylpropanesulfonic acid and their alkali salts, trimethyl-2-(1-(meth)acrylamido-1,1-dimethylethyl)ammonium chloride, trimethyl-3-(1 It is also possible to have a small proportion of cationic monomers such as -(meth)acrylamidopropyl)ammonium chloride, 1-vinyl-2-methylimidazole, and primary to quaternized products thereof. In modified PVA which is a saponified product of a copolymer of (A) vinyl ester used in the present invention and an olefinic unsaturated monomer having a silyl group in the molecule represented by the above general formula () or (). The content of silyl groups is required to be 0.1 to 2.5 mol% as monomer units containing silyl groups. The degree of saponification is usually preferably in the range of 70 to 100 mol%. Further, the degree of polymerization is usually selected from the range of 10 to 3000. When dissolving the modified PVA used in the present invention in water, usually after dispersing the modified PVA in water, an alkali such as sodium hydroxide is added in some cases, and the mixture is heated while stirring. This makes it possible to obtain a homogeneous aqueous solution. The inorganic substance (B) used in the present invention includes:
Water-insoluble inorganic substances containing aluminum, silicon, magnesium or calcium elements are used,
Specifically, clay, talc, calcium carbonate, aluminum silicate, calcium silicate, silica,
Examples include sand and aluminum oxide. Incidentally, water-soluble silicates such as water glass, water-soluble aluminum compounds such as aluminum sulfate and sodium aluminate, water-soluble zirconium compounds such as zirconium ammonium carbonate, etc.
(A) A saponified product of a copolymer of a vinyl ester and an olefinic unsaturated monomer having a silyl group in the molecule represented by the following general formula () or (), which is a monomer having a silyl group in the molecule. mass unit
It is not preferably used because it tends to increase the viscosity of a modified PVA aqueous solution containing 0.1 to 2.5 mol%. For purposes of the present invention, water-insoluble inorganic particles are preferred. There are no particular restrictions on the particle size of the inorganic particles, and various types can be used depending on the application, but in the case of applications that require transparency and surface smoothness, particles with a small particle size are generally preferred.
A particle size of 0.05 to 200 mμ is adopted, and for other uses, particles with a large particle size are preferred. In the composition of the present invention, (A) a saponified product of a copolymer of a vinyl ester and an olefinic unsaturated monomer having a silyl group in the molecule represented by the general formula () or (), The weight mixing ratio of modified PVA containing 0.1 to 2.5 mol% of monomer units having a silyl group in the molecule and (B) a water-insoluble inorganic substance containing aluminum, silicon, magnesium or calcium elements is (A) /(B)=1/99～
It's 90/10. If the blending ratio of (B) is less than 10, the water resistance will not be sufficient, and if it exceeds 99, the strength of the composition will decrease. As mentioned above, the composition of the present invention is a saponified product of a copolymer of (A) a vinyl ester and an olefinic unsaturated monomer having a silyl group in the molecule represented by the general formula () or (). (B) a water-insoluble inorganic substance containing aluminum, silicon, magnesium, or calcium elements; ) and (B) weight ratio is (A)/(B)=1/
The essential condition is that the ratio is 99 to 90/10, but in addition to this, solvents, various additives, other water-soluble resins, polymer aqueous dispersions, etc. can be included depending on the purpose. Water is preferably used as a solvent, but it can also be used in combination with various solvents such as alcohols, ketones, dimethylformamide, dimethyl sulfoxide, etc. As additives, various antifoaming agents, various dispersants, nonionic Examples of water-soluble resins include cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, poly(meth)acrylic acid, polyhydroxy(meth)acrylate, etc. Copolymers thereof, (meth)acrylic polymers such as polyacrylamide, polyvinylpyrrolidone or copolymers thereof, modified PVA containing carboxy groups, modified PVA containing sulfate groups, modified PVA containing sulfonic acid groups, modified PVA containing phosphoric acid groups , modified PVA containing a quaternary ammonium base, modified PVA containing an amino group, and PVA derivatives such as general PVA. Furthermore, examples of the aqueous polymer dispersion include aqueous dispersions of acrylic polymers and copolymers, ethylene-vinyl acetate copolymers, vinyl ester polymers and copolymers, styrene-butadiene copolymers, and the like. The composition of the present invention is dissolved or dispersed in water or water containing the above-mentioned organic solvent, and is preferably used as an aqueous dispersion. The composition of the present invention is made of modified PVA having a specific amount of specific silyl groups, and has reactivity towards inorganic substances, and by taking advantage of this performance, film-forming property, film strength, and water resistance, it can be used as an adhesive for inorganic or organic substances. It is effectively used as a binder, a paint vehicle, a treatment agent for inorganic or organic materials, such as a surface coating agent, and is also used in applications where water-soluble resins have conventionally been used, such as films and sheets. Among these, the composition of the present invention has a particularly strong reactivity with inorganic substances, so it shows excellent adhesion to inorganic substances, and also shows excellent water resistance, so it can be used as a treatment agent for inorganic materials, such as cement and mortar. It is extremely useful as a surface treatment agent for inorganic materials. The reason why the composition of the present invention has excellent film-forming properties, film strength, and water resistance is not fully understood, but the specific silyl group in the molecule used in the composition of the present invention has been identified. Modified PVA with amount
The vinyl ester unit or vinyl alcohol unit in the PVA exhibits film-forming properties, and the silyl group to which an alkoxyl group or acyloxyl group is bonded, or the silanol group or its salt, which is a hydrolyzed product of these, can be used as an inorganic or modified PVA. is highly reactive with hydroxyl groups, silanol groups, or salts thereof, and these react with each other to form a strong coating, which is presumed to provide high coating strength or water resistance. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. In the examples, unless otherwise specified, "%" and "part" represent weight standards. Example 1 A copolymer of vinyltrimethoxysilane and vinyl acetate was saponified to contain 0.5 mol% of silyl groups as vinyl silane units, with a degree of saponification of the vinyl acetate unit of 99.2 mol% and a degree of polymerization of 1600. A modified PVA containing groups was obtained. Denature this denatured PVA
A 10% aqueous solution of modified PVA was prepared by dissolving PVA in water containing 2.5% sodium hydroxide. 30 parts of clay slurry decomposed in water to give a solid content of 30% was mixed with 100 parts of this aqueous solution, and this aqueous dispersion was cast to form a sheet-like product. The obtained sheet-like material was also insoluble in cold water and hot water (95°C). Comparative Example 1 A sheet-like product was obtained in the same manner as in Example 1, except that PVA with a degree of polymerization of 1750 and a degree of saponification of 98.5 mol % was used instead of the modified PVA used in Example 1.
When this sheet-like material was immersed in water, it was redispersed into pieces. Examples 2 to 4 The same procedure as in Example 1 was carried out except that the following inorganic substances were used in place of the clay used in Example 1.
The obtained sheet-like material was also insoluble in cold water and hot water (95°C). Inorganic substance used in Example 2: White carbon (silica) Inorganic substance used in Example 3: Calcium carbonate Inorganic substance used in Example 4: Calcium silicate Example 5 Dimethyl-3-methacrylamidopropyl-
A copolymer of 3-trimethoxysilylpropylammonium chloride and vinyl acetate was saponified to produce a modified product containing 0.25 mol% of silyl groups, a degree of saponification of vinyl acetate units of 98.5 mol%, and a degree of polymerization of 1750.
Got PVA. Example 1 Using this modified PVA
When the same procedure as above was carried out, the obtained sheet-like material was found to be insoluble in both cold water and hot water (95°C). Example 6 A copolymer of vinyltriisopropoxysilane and vinyl acetate was saponified to contain 0.3 mol% of silyl groups.
A silyl group-containing PVA with a degree of saponification of vinyl acetate units of 88 mol % and a degree of polymerization of 1750 was obtained. Dissolve this modified PVA to create a 10% aqueous solution,
50 parts of this aqueous solution, 100 parts of sand (Toyoura standard sand) and 100 parts of water.
A slurry was prepared. The resulting slurry was cast onto a slate to a dry solid content of 30 g/m ² and dried at room temperature for 3 days to form a film. A funnel to which a glass tube was connected was adhered onto the coating, and water permeability into the coating was measured while filling the glass tube with water so that the water level was always maintained at 1 m. Water permeation amount was 10 ml/m ² for 15 days. Comparative Example 2 When the water permeability of the slate itself used in Example 6 was measured in the same manner as in Example 6, it was found to be 5000ml/
It was ^m2 . Comparative Example 3 Silyl group-containing modified PVA used in Example 6
The same procedure as in Example 6 was conducted except that PVA with a degree of polymerization of 1750 and a degree of saponification of 98.5 was used instead. The water permeability is
It was 5000ml/ ^m2 . Example 7 10% aqueous solution of modified PVA used in Example 1
A slurry of 100 parts of white carbon dispersed in water was added to 100 parts to create an aqueous dispersion with a solid content of 10%. This aqueous dispersion was applied to a mortar plate having a surface pH of 12 at a dry solid content of 50 g/m ² , a cotton cloth was placed thereon as a reinforcing agent, and the mixture was dried at room temperature for 2 days. After that, apply 1 cm to the coating on the mortar board.
Make a slit with a knife at the width of the
After being immersed in water at 40°C for 3 days, the water-resistant adhesive strength was measured using an autograph (Shimadzu Model IM-100) at a peeling angle of 90° and a pulling speed of 500 mm/min, and the results shown in Table 1 were obtained. Comparative Example 4 The same procedure as in Example 7 was conducted except that the 10% aqueous solution of modified PVA used in Example 7 was used and white carbon was not used. The results are shown in Table 1. Comparative Example 5 The same procedure as in Example 7 was carried out except that instead of the modified PVA used in Example 7, ordinary unmodified PVA with a degree of polymerization of 1750 and a degree of saponification of 98.5 was used. The results are shown in Table 1.

Table 1 shows that the water-resistant composition of the present invention has excellent water resistance even under alkaline conditions. Example 8 The modified PVA obtained in Example 1 was dissolved in water containing 2.5% sodium hydroxide based on the modified PVA to prepare a 10% aqueous solution of the modified PVA. To 100 parts of this aqueous solution, 30 parts of clay dispersed in water (solid content)
Alternatively, add 100 parts of white carbon (solid content) dispersed in water and add adjustment water as appropriate to achieve a solid content of 30% [PVA/clay = 1/3] and 10% [PVA/white carbon = 1]. /10] was prepared. This aqueous dispersion was cast and dried at 100° C. for 1 hour to prepare a sheet. This sheet-like material was immersed in water at 20° C. for 24 hours, and the degree of swelling and solubility were measured. The degree of swelling and solubility were determined using the following formulas. Swelling degree (parts) = Weight of sample after swelling - Weight of sample after further drying after swelling / Weight of sample after further drying after swelling Solubility (%) = (1 - Weight of sample after further drying after swelling / The above aqueous dispersion was applied to a mortar plate with a surface pH of 12 at a dry solid content of 50 g/m ² (sample weight before swelling) x 100, and a cotton cloth was placed on top as a reinforcing material for 2 days. Dry at room temperature. After that, a 1 cm wide cut was made with a knife in the coating on the mortar board, and after soaking in 40℃ water for 3 days, Autograph (Shimadzu Corporation)
IM-100 type), peel angle 90°, tensile speed 500
Water resistant adhesion was measured in mm/min. The results are also shown in Table 2. Comparative Example 6 77.4 g (0.90 mol) of vinyl acetate and 8.8 g (0.10 mol) of methyl methacrylate were mixed with 0.16 g of α,α′-azobisisobutyronitrile (AIBN) as an initiator.
Copolymerization was carried out at 60°C to obtain 34.5 g of copolymer. Vinyl acetate in the copolymer was 89 mol%. This polymer was dissolved in a mixed solvent of acetone and methanol (1:1 by volume) and saponified by adding 0.2N caustic soda. The saponification degree of vinyl acetate unit is 99.1
It was in mol%. Dissolve 1 part of this saponified product in 35 parts of water, and this contains 0.086 part of acetic acid II-water salt.
Add 1.4 parts of 28% ammonia water and shake for 1 minute,
It was left at room temperature for 24 hours. Using this aqueous solution, a sheet-like material was prepared in the same manner as in Example 8, and the swelling degree and
Solubility was measured. Further, this aqueous solution was applied onto a mortar board in the same manner as in Example 8, and the water-resistant adhesive strength was measured. The results are shown in Table 2. Comparative Example 7 An aqueous dispersion was prepared by mixing and dissolving 8 parts of PVA with a degree of saponification of 88 mol% and a degree of polymerization of 1830, 2 parts of silica from a metal silicon electric furnace, and 90 parts of water. Using this, the degree of swelling, solubility, and water-resistant adhesive strength of the sheet to a mortar plate were measured in the same manner as in Example 8. The results are shown in Table 2. Comparative example 8 10% fully saponified PVA (PVA-117 manufactured by Kuraray)
A 35% emulsion was prepared by emulsion polymerization of vinyl acetate monomer in an aqueous solution. 60 parts of Katsukoyama T-clay were thoroughly mixed with 100 parts of this emulsion, and 6 parts of a 10% aqueous hydrochloric acid solution was added to prepare an aqueous dispersion having a pH of 1.2. Using this, the degree of swelling, solubility, and water-resistant adhesive strength of the sheet to a mortar plate were measured in the same manner as in Example 8. The results are shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1 (A) A saponified product of a copolymer of a vinyl ester and an olefinic unsaturated monomer having a silyl group in the molecule represented by the following general formula () or (), A modified polyvinyl alcohol containing 0.1 to 2.5 mol% of a monomer unit having a silyl group in the molecule, and (B) a water-insoluble inorganic substance containing aluminum, silicon, magnesium or calcium elements, and (A). The weight mixing ratio of (B) is (A)/(B)=1/
A water resistant composition characterized in that it has a water resistance of 99 to 90/10. [Here, n is an integer of 0 to 4, m is an integer of 0 to 2, R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is an alkoxyl group or acyloxyl group having 1 to 40 carbon atoms (here, an alkoxyl group) , the acyloxyl group may have an oxygen-containing substituent). ] [Here, m is an integer of 0 to 2, R ¹ is a carbon number of 1 to
5 alkyl group, R ² is an alkoxyl group or acyloxyl group having 1 to 40 carbon atoms (the alkoxyl group or acyloxyl group may have an oxygen-containing substituent), R ³ is a hydrogen atom or a methyl group , R ⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkylene group having 1 to 5 carbon atoms, or a divalent organic residue in which chain carbon atoms are interconnected by oxygen or nitrogen. show. 2. The water-resistant composition according to claim 1, wherein the composition is a composition for treating inorganic materials.